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UNIVERSITY  OF  ILLINOIS  LIBRARY  AT  URBANA-CHAMPAIGN 


L161— 0-1096 


PROPERTIES  OF  MIXTURES  OF  NOR- 
MAL BUTYL  ALCOHOL  AND  WATER; 
RECOVERY  OF  NORMAL  BUTYL 
ALCOHOL  FROM  WATER 
MIXTURES 

BY 

CLARENCE  FRANCIS  CROSSLEY 


THESIS 

FOR  THE 

D E G R E E O F FiAGHE  L O R O F S C I E NGE 

IN 

CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 

UNIVERSITY  OF  ILLINOIS 


1922 


UNIVERSITY  OF  ILLINOIS 


May  51, 


.192 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 


Clarence  Francis  Crossley 


ENTITLED  Properties  of  Mixtures  or  formal  Butyl  Alcohol  and 


Water;  Recovery  of  Normal  Butyl  Alcohol  from  Water  Mixtures 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 


DEGREE  OF  Bachelor  of  Science  in  Chemistry 


ACTIFGr  HEAD  OF  DEPARTMENT  OF  -CHEMISTRY-: 


. 


%■ 


Table  of  Contents. 


Acknowledgment 

I.  Introduction 

II.  Dehydration  of  Uormal  Buty}  Alcohol 

III.  Density  of  Alcohol-Water  Mixtures 

IV.  Boiling  Points  of  Alcohol-Water  Mixtures 

V.  Fractional  Distillation 

VI.  Summary 

VII.  Bibliography 


Page . 

1. 

2. 

4. 

5. 
8. 

10. 

11. 

12. 


. 


• » 


1. 


Acknowledgment 

The  writer  wishes  to  express  his  sincere 
thanks  and  appreciation  to  hr.  J.E. Reedy  who  ren- 
dered advice  and  aid  at  all  times  and  made  the 
completion  of  this  work  possible. 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/propertiesofmixtOOcros 


2 


I.  Introduction. 

normal  butyl  alcohol  is  becoming  more  and 
more  important  in  organic  chemistry,  especially  as 
a solvent  for  various  substances  and  the  recovery 
of  this  solvent  promises  to  develop  into  an  import- 
ant consideration  in  commercial  use.  It  was  with 
this  idea  in  mind  that  the  following  work  was  done 
concerning  the  physical  properties  and  recovery  of 
the  normal  butyl  alcohol. 

Until  quite  recently,  very  little  was  to  be 
found  in  the  literature  concerning  this  alcohol  and 
the  writer  feels  that  the  work  is  among  the  first 
that  have  been  done  on  this  subject.  Hereafter  in 
this  article  the  word  alcohol  will  be  used  to  denote 
normal  butyl  alcohol  only. 

Uormal  butyl  alcohol  is  manufactured  by  a fer- 
mentation process  in  which  acetone  and  alcohol  , par- 
ticularly butyl  alcohol,  are  obtained  by  fermentation 
under  aerobic  or  anaerobic  conditions  of  carbohydrate 
material  such  as  maize,  rice,  wheat,  oats,  potatoes, 
etc.,  with  a culture  of  the  bacteria  which  are  found 
in  soil  or  on  cereals  such  as  maize,  rice  and  flax. 
The  bacteria  will  also  liquefy  gelatin  and  are  stated 
to  be  probably  Bacillus  granulobacter  pectinovorum. 


T 


. 


3. 

The  production  of  this  alcohol  is  now  carried 
on  at  a comparatively  low  cost.  The  price  in  1917 
was  $2.10  for  10  grams  and  now  the  cost  is  only  $5.00 
per  gallon. 


' 


4. 


II.  Dehydration  of  Normal  Butyl  Alcohol. 

In  making  anhydrous  alcohol,  the  following  pro- 
ceedure  was  used.  The  usual  method  of  treatment  with 
lime  was  first  used.  The  alcohol  refluxdd  with  fresh 
lime  for  several  hours  and  then  distilled  through  an 
efficient  rectifying  column.  This  was  then  refluxed 
over  metallic  calcium  and  the  distillation  through  the 
rectifying  column  repeated  until  a constant  boiling 
point  was  obtained.  It  is  believed  that  alcohol  so 
prepared  contains  only  a small  fraction  of  one  per 
cent  of  water.  This  small  quantity  of  waterwould  not 
make  an  appreciable  error  in  the  specific  gravity 
determinations  of  the  alcohol-water  mixtures. 

The  partial  dehydration  by  means  of  lime  gives 
an  alcohol  of  about  99.5  % and  for  all  practical  pur- 
poses this  is  probably  pure  enough.  However,  in  or- 
der to  obtain  a purer  product,  the  alcohol  is  reflux- 
ed over  metallic  calcium  and  redistilled.  This  re- 
moves all  the  water. 

No  satisfactory  test  was  found  for  the  detect- 
ion of  slight  amounts  of  water  in  the  alcohol.  The 
copper  sulfate  test  was  found  to  be  indecisive  while 
the  benzene  test  could  not  detect  water  unless  the 
water  was  present  in  an  amount  greater  than  5 %. 


. 


. 


. 


i 


5 


III.  density  of  Alcohol-Water  Mixtures. 


The  alcohol-water  mixtures  were  ma&e  by 
weighing  the  water  and  alcohol  in  stoppered  bottles. 

The  stoppers  were  then  made  secure  and  the  solutions 
thoroughly  mixed  for  several  hours  by  means  of  a 
mechanical  shaker  which  insured  complete  solution  of 
the  respective  liquids  in  each  other. 

Then  the  specific  gravity  was  determined  of  the 
solutions  in  each  bottle  in  which  only  one  layer  was 
present.  A Westphal  balance  was  used  for  the  specific 
gravity  determinations.  The  alcohol  will  dissolve 
19.8  $ of  water  and  v/ater  will  dissolve  7.25  % alcohol. 

The  results  of  these  determinations  are  shown 
belowr . 


Water  layer. 


wt.  % 

alcohol 

sp.  gr 

1.62 

0.9962 

2.29 

0.9950 

2.21 

0.9920 

2.97 

0.9927 

Wt.  # 

alcohol 

sp,  gr 

4.71 

0.9911 

6.22 

0.9888 

6.98 

0.9880 

» 

* 


t 


. . 


. 


6 


Alcohol  layer. 


YIt.fo 

alcohol 

sp.  gr 

98.1 

0.8100 

96.6 

0.8130 

93.4 

0.8191 

92.2 

0.8210 

90.8 

0.8248 

89.3 

0.8275 

\U.%  ale. 

sp.  gr 

87.8 

0.8298 

86.5 

0.8322 

85.7 

0.8345 

82.8 

0.8390 

80.2 

0.8445 

These  results  were  plotted  on  cross-section 
pa$er  ( Hates  I and  II  ) so  that  0.1  ^cjsald  be 
easily  read  on  the  abscissa  and  0.0002  sp.gr.  on 
the  ordinate.  A straight  line  curve  was  drawn  to 
connect  the  points  and  from  these  Table  I was  con- 
structed, giving  the  specific  gravity  for  each  per- 
centage by  weight  of  alcohol  and  the  corresponding 
volume  percentage. 


7 


Table  I. 

Specific  Gravity  of  Normal  Butyl  Alcohol-Water  Mixtures. 
Wt.  % VoT.  % Wt.  % Vol . °/o 


ale  ohol 

ale . 

sp.  gr. 

ale . 

ale . 

sp.  gr 

0 

0.0 

0.9984 

100 

100 

0.8063 

1 

1.2 

0.9969 

99 

99.3 

0.8082 

2 

2.5 

0.9953 

98 

98.5 

0.8103 

3 

3.7 

0.9939 

97 

97.6 

0.8121 

4 

4.9 

0.9923 

96 

96.8 

0.8140 

5 

6.1 

0.9910 

95 

95.9 

0.8160 

6 

7.3 

0.9895 

94 

95.1 

0.8179 

7 

8.6 

0.9fi£>0 

93 

94.3 

0.8199 

7.25 

8.8 

0.9878 

92 

93.4 

0.8218 

91 

92.6 

0.8258 

- 

90 

91.8 

0.8256 

89 

91.0 

0.8275 

88 

90.1 

0.8295 

87 

89.3 

0.8314 

86 

88.4 

0.8333 

85 

87.5 

0.8352 

84 

86.7 

0.8372 

83 

85.8 

0.8391 

82 

85.0 

0.8410 

81 

84.1 

0.8430 

80.2 

83.2 

0.8445 

8 


IV.  Boiling  Joints  of  Alcohol-Water  Mixtures. 

The  same  solutions  that  were  used  for  the  det- 
ermination of  the  specific  gravities  were  also  used 
for  the  determination  of  the  boiling  points  of  sol- 
utions of  varying  concentration.  The  solution  was 
placed  in  a flask  which  was  fitted  with  a condenser 
in  order  to  keep  the  concentration  of  the  liquid  con- 
stant. The  boiling  point  was  taken  and  corrections 
made  for  pressure  differences  from  760  mm,  for  stem 
exposure,  and  for  calibration  of  the  thermometer  used. 

The  thermometer  was  calibrated  with  water  and  a 
constant  correction  of  + 0.4°  found.  The  observed 
temperatures  were  corrected  for  exposed  mercury  col- 
umn by  adding  IT ( t-t'  ). 0)00154,  where  N is  the  length 
of  the  exposed  mercury  in  degrees,  t the  observed 
temperature,  and  t’  the  room  temperature.  A correction 
for  pressure  was  calculated  from  dT  = CT-g  ( 760  - P ) 
where  dT  is  the  correction,  0 a constant,  Tg  the  boil- 
ing point  of  the  liquid,  and  P the  observed  pressure. 

Table  II  shows  the  data  in  tabular  form  and  the 
experimental  values  were  used  to  construct  the  boil- 
ing point  curve  which  is  shown  on  the  graph  paper 
f Plate  III). 


1 

. 

. 

• 

' 

9 


Table  II. 

Boiling  Joints  of  Alcohol-Water  Mixtures. 


Sp . Gr . 
( curve ) 

o 
• H 

+>  ca 

Es 

B.  P. 

( obs ) 

Corr . 

B.  P. 

( corr) 

0.9984 

0.0 

98.7 

1.30 

100.00 

0.9960 

1.63 

97.8 

1.27 

99.07 

0.9947 

2.39 

96.3 

1.24 

97.54 

0.9935 

3.21 

95.1 

1.28 

96.38 

0.9924 

3.97 

94.4 

1.20 

95.60 

0.9915 

4.71 

93.7 

1.18 

94.88 

0.9891 

6.22 

92.8 

1.16 

93.96 

0.9880 

6.98 

92.2 

1.16 

93 .36 

Mixt.  both 

layers 

92.1 

1.16 

93.26 

0.8100 

98.1 

108.0 

2.24 

110.24 

0.8130 

96.6 

103.0 

2.00 

105.0 

0.8191 

93.4 

97.0 

2.00 

99.0 

0.8214 

92.2 

94.8 

1.93 

96.73 

0.8240 

90.8 

93.6 

1.90 

95.50 

0.8270 

89.3 

92.6 

1.87 

94.47 

0.8298 

87.8 

92.0 

1.87 

93.87 

0.8325 

86.5 

91.8 

1.86 

93.66 

0 . 8340 

85.7 

91.8 

1.86 

93.66 

0.8395 

82.8 

91.4 

1.85 

93.25 

0.8445 

80.2 

91.3 

1.94 

93.24 

0.9984 

0.0 

98.0 

2.00 

100.00 

10. 


VI.  Fractional  Distillation. 

I’he  alcohol  is  recovered  from  the  water  mixtures 
by  means  of  fractionation  through  an  efficient  rect- 
ifying column.  In  a trial  run,  large  amounts  of  alc- 
ohol and  water  were  thoroughly  mixed  and  750  cc  of 
the  top  layer  were  taken  for  the  determination.  This 
layer  contained  80.2  per  cent  alcohol.  The  first 
portions  of  the  distillate  contained  40  per  cent  of 
water  as  conpared  to  20  per  cent  in  the  original 
liquid  in  the  flask.  This  proportion  remained  con- 
stant until  all  the  water  distilled  over  and  then 
the  pure  alcohol  was  collected. 

The  top  layers  of  each  portion  were  mixed  and 
the  fractionation  repeated,  giveng  more  of  the  pure 
liquid.  Then  the  water  layers  from  each  portion 
were  added  together  and  distilled  and  all  the  alc- 
ohol came  over  quickly  in  an  80.2  per  cent  mixture. 
This  was  added  to  the  other  portions  rich  in  alco- 
hol and  the  distillation  carried  out  a third  time. 

The  time  required  for  the  distillations  is  not 
excessive  and  four  distillations  yield  about  90  per 
cent  of  the  alcohol  in  the  original  mixture  in  a 
pure  form. 


. 


.. 


. 


' 


. 


11. 


VI.  Summary. 

1.  The  specific  gravity  of  normal  butyl  alcohol 

was  found  to  be  0.8064  at  25°  8.  Tobin 
gives  0.8057  and  Wad  and  Gokhale  0.8066. 

2.  The  boiling  point  was  found  to  be  117.4°  at 

760  mm  pressure,  loroshevski  and 
Dvorzhanchik  give  117.1°,  Kahlbaum  gives 
117.6°,  and  Tobin  gives  117. 71°, 

3.  Tables  for  specific  gravities  and  for  boiling 

points  of  alcohol-water  mixtures  are  given. 

4.  The  alcohol  is  only  partially  miscible  with  water. 

Two  layers  are  formed  which  contain  80.2 
per  cent  and  7.25  per  cent  of  alcohol. 

5.  Curves  for  specific  gravities  and  for  boiling 

points  of  the  varying  concentrations  are 
given. 

6.  The  alcohol  may  be  recovered  from  water  mixtures 

by  fractionation. 


12 


VII.  Bibliography. 

1.  Roger  3P.  Brunei,  J.L. Crenshaw,  and  Blise  Tobin. 

J.  Am.  Chem.  Soc.  43,  561-77  ( 1921  ). 

2.  Y.  B.  Wad  and  A.  G.  gokhale. 

J.  Ind.  Inst.  Sei.  4,  17-25  ( 1921  ). 

3.  Kahlbaum. 

Z.  physik.  ohem.  46,  628  and  646  (1898). 

4.  Boroshevski  and  Bvorzhanchik. 

G.  A.  3,  1355  (1909). 

5.  C.  Weizmann. 

G.A.  13,  1595  (1909). 

6.  Horace  B.  Speakman. 

J.  Soc.  Chem.  Ind.  38,  155-617. 

7.  Kennedy  J.  p.  Orton  and  Bavid  C.  Jones. 

J.  Chem.  Soc.  114.  1194. 

8.  R.  Seligman  and  P.  Williams. 

J.  Soc.  Chem  Ind.  37,  159-657. 

9.  Vashburn’s  Principles  of  Physical  Chemistry. 


